Copper-catalyzed synthesis of cyclopropyl bis(boronates) from aryl olefins and carbon monoxide

Abstract

Cyclopropanes, especially substituted cyclopropanes play important roles in many pharmaceuticals and organic synthesis. In this communication, we introduced a new strategy for the synthesis of diborylated cyclopropanes via a copper-catalyzed...

Copper-Catalyzed Synthesis of Multideuterium-Labeled Alcohols from Styrenes with CO and D2 as the Source of the Hydroxymethyl Group

“…Based on these experimental results and literature precedent, ,, the proposed mechanism of this reaction of styrenes is shown in Figure . Initially, the (L)­Cu–D complex was produced in the presence of NaO t Bu and D 2 .…”

“…Recently, our group developed several copper-catalyzed organic transformations with CO as the carbon or carbonyl source. , In our latest work on Cu-catalyzed carbonylation reactions, we found that carbon carbene species can be formed as key intermediates and were ready for further transformations . Hence, we believe that the carbene species III , which isomerizes from the acyl copper complex via a three-membered-ring state, can also be captured by D 2 .…”

Carbon Monoxide as C1 Building Block in Fine Chemical Synthesis†

“…Conveniently substituted cyclopropanes are commonly found in many pharmaceuticals, and may act as intermediates in organic synthesis. [ 148 ] In this regard, Wu [ 149 ] reported an innovative synthesis of diborylated cyclopropanes via a copper‐catalyzed carbonylation process using copper(II) triflate/dppp as catalyst, followed by cyclopropanation (Scheme 83). This reaction was effectively carried out using both internal or terminal aryl olefins, which allowed to prepare in moderate yields (34%—57%), a family of cyclopropyl bis(boronates) (18 examples), with a completely defined stereochemistry.…”

Copper-catalyzed synthesis of β-boryl cyclopropanesvia1,2-borocyclopropanation of aryl olefins with CO as the C1 source

“…1d). We could obtain a range of different products through the transformations of the in situ generated carbene intermediates including α-C–H insertion, 32 β-C–H insertion, 33,34 CO insertion, 35 and N–H/O–H insertion of carbene. 36…”

“…1d). We could obtain a range of different products through the transformations of the in situ generated carbene intermediates including a-C-H insertion, 32 b-C-H insertion, 33,34 CO insertion, 35 and N-H/O-H insertion of carbene. 36 With our continued interest in copper-catalyzed borocarbonylation of olens, we speculate that the carbene intermediates can be captured by C]C double bonds to generate cyclopropanes.…”